EP1260535A1 - Water-soluble polymers from esters of acrylic acid and alkylpolyalkylene glycols - Google Patents

Water-soluble polymers from esters of acrylic acid and alkylpolyalkylene glycols Download PDF

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Publication number
EP1260535A1
EP1260535A1 EP02009116A EP02009116A EP1260535A1 EP 1260535 A1 EP1260535 A1 EP 1260535A1 EP 02009116 A EP02009116 A EP 02009116A EP 02009116 A EP02009116 A EP 02009116A EP 1260535 A1 EP1260535 A1 EP 1260535A1
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Prior art keywords
water
polymerization
weight
mixture
esterification
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German (de)
French (fr)
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EP1260535B1 (en
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Matthias Dr. Kroner
Karl-Heinz Büchner
Gregor Dr. Brodt
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0053—Water-soluble polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0059—Graft (co-)polymers
    • C04B2103/006—Comb polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/408—Dispersants
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/52—Grinding aids; Additives added during grinding

Definitions

  • the present invention relates to water-soluble polymers of esters from acrylic acid and alkyl polyalkylene glycols, which are obtainable by azeotropic esterification of a mixture of Acrylic acid and alkyl polyalkylene glycol in a molar ratio of 2 to 3: 1 in the presence of an organic solvent mixed with water forms an azeotrope, at least 85 wt .-%, based on the Alkyl polyalkylene glycol, and subsequent radical polymerization of the mixture obtained in the esterification in aqueous Medium, using the organic solvent during the Polymerization distilled off azeotropically from the reaction mixture and the distilled water returns to the mixture or replaced with fresh water.
  • the invention also relates to the preparation of the polymers and their use as an additive to cementitious systems, in particular as a condenser and grinding aid.
  • Water-soluble polymers based on polycarboxylic acid alkyl polyalkylene glycol esters are due to their particularly good Dispersion of cement in aqueous suspensions of increasing technical interest in the construction industry, where it acts as a plasticizer be used. You solve the previous ones Concrete plasticizer based on melamine or naphthalene-formaldehyde sulfonates as it has a significantly higher dispersibility have.
  • EP-A-989 108 discloses dispersants for concrete based on polymeric esters of acrylic acid and methylpolyethylene glycol, which are obtained by azeotropic esterification of acrylic acid and methylpolyethylene glycol (M w 472) in a molar ratio of 3.35: 1 in cyclohexane, followed by replacement of the cyclohexane by added water can be prepared by azeotropic distillation and polymerization of the resulting 80 wt .-% aqueous ester solution in water.
  • This is a three-stage manufacturing process in which problems with the contamination of the apparatus by co-distilled acrylic acid also occur in the distillation step, which is why the addition of a polymerization inhibitor to the cooler is necessary.
  • the compounds thus obtained show unsatisfactory application properties.
  • the object of the invention was to provide concrete plasticizers, which is characterized by advantageous application properties distinguish, in particular across the entire processing chain of Ready-mix concrete, i.e. during manufacturing, transportation and Processing time, a constant liquefaction effect have, and are economical to produce.
  • the excess that does not react with the alkyl polyalkylene glycol Acrylic acid remains in the one obtained during the esterification Mixture and reacts as a comonomer in the subsequent radical polymerization.
  • esterification can be beneficial to add to the esterification to acrylic acid up to 0.5 mol of another monoethylenic unsaturated carboxylic acid, or a carboxylic acid derivative such as maleic acid, maleic anhydride or fumaric acid, be used.
  • carboxylic acid derivative such as maleic acid, maleic anhydride or fumaric acid
  • the azeotropic esterification of acrylic acid with the alkyl polyalkylene glycol takes place in the presence of an organic solvent, that forms an azeotrope with water, and can be according to known Procedures are made.
  • the organic solvent is also referred to as an entrainer. With the azeotropic Esterification causes the water formed during the reaction to become azeotropic removed from the reaction mixture.
  • the esterification is carried out at least until sales of 85% by weight, preferably at least 90% by weight, based on the Alkyl polyalkylene glycol, is reached.
  • the turnover can be based on decrease in acid number (acrylic acid) or OH number (A1-kylpolyalkylenglykol) of the reaction mixture are followed.
  • acid number acrylic acid
  • OH number A1-kylpolyalkylenglykol
  • the molecular weight M w of the alkyl polyalkylene glycols is generally 350 to 4000, preferably 500 to 2000, particularly preferably 750 to 1500 and very particularly preferably approximately 1000.
  • Alkyl polyethylene glycols are particularly preferred and very particularly preferably methyl polyethylene glycols of the molecular weights mentioned used.
  • alkyl (especially Methyl) polyalkylene glycols suitable, the units of Propylene oxide and / or butylene oxide in combination with units of ethylene oxide.
  • the same units can be used in blocks or be statistically arranged.
  • partially etherified polytetrahydrofuran which, on one side, carries an alkyl group, preferably a C 1 -C 4 alkyl group, as the end group.
  • the effectiveness of the copolymers in the respective cementitious system can sometimes be increased if mixtures of alkyl polyalkylene glycols can be used with different molecular weights.
  • the esterification is expediently carried out in the presence of a catalyst.
  • All organic and inorganic acids can be used as catalysts.
  • suitable acidic catalysts are sulfuric acid, sulfurous acid, di- and polysulfuric acid, sulfur trioxide, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, C 2 -C 30 alkylbenzenesulfonic acids, sulfuric acid monoesters of C 1 -C 30 alcohols and alkylpolyalkylene glycolic acid, phosphoric acid , hypophosphorous acid, polyphosphoric acid, hydrochloric acid, perchloric acid and acidic ion exchangers.
  • P-Toluenesulfonic acid and methanesulfonic acid are preferred, p-toluenesulfonic acid is particularly preferred.
  • the amount of catalyst based on the total of acrylic acid and alkyl polyalkylene glycol is generally up to 10 % By weight, preferably 0.05 to 7% by weight and particularly preferably 0.1 up to 5% by weight.
  • Suitable organic entrainer during esterification Solvents are aliphatic (isoaliphatic and linear aliphatic), cycloaliphatic, aliphatic-aromatic and pure aromatic hydrocarbons.
  • the boiling point is particularly suitable organic solvent is usually 60 to 300 ° C, preferably at 70 to 150 ° C.
  • Aromatics such as benzene, toluene, o-, m- and p-xylene, xylene mixtures, Trimethylbenzene, tetramethylbenzene, mesitylene, ethylbenzene, isopropylbenzene, n-butylbenzene and isobutylbenzene.
  • Cyclohexane, methylcyclohexane, toluene and xylene mixtures are preferred and o-xylene, with toluene being particularly preferred.
  • boiling-point petrol is a gasoline with a boiling range of 90 up to 100 ° C, 100 to 140 ° C and 140 to 160 ° C.
  • the groups can depending on origin, purely linear aliphatic, purely isoaliphatic, purely aliphatic-aromatic or purely aromatic constituents contain.
  • the entrainer forms an azeotropic together with water Mixture that is usually a boiling point below that of the lower boiling component.
  • the boiling points of the Azeotropic mixtures are preferably in the range from 70 to 130 ° C.
  • the proportion of entrainer in the reaction mixture is usually 5 to 50% by weight, preferably 10 to 40% by weight, based on the sum of acrylic acid and alkyl polyalkylene glycol.
  • the amount of entrainer is advantageous according to the invention chosen so that the entrainer in the reaction mixture Boiling point of 100 to 150 ° C, preferably 110 to 140 ° C, has.
  • the boiling points of the azeotropes and the entrainer are in the the mixture present in the esterification is usually higher than that of the pure substances.
  • the alkyl polyalkylene glycol which is end-capped at one end can protect against oxidative degradation during the esterification if desired, reducing agents are added.
  • Suitable reducing agents are e.g. Phosphorus compounds such as hypophosphorous Acid and phosphorous acid and sulfur compounds such as Sulfur dioxide, thiosulfate and dithionite. Of course you can reducing agent mixtures are also used.
  • the amount is in generally up to 5% by weight, preferably up to 2% by weight, based on Alkylpolyalkylene.
  • the amount of inhibitor is 0.001 to 2% by weight, preferably 0.005 to 0.5% by weight, based on the acrylic acid.
  • the esterification is usually at 80 to 200 ° C, preferably at 90 to 170 ° C and particularly preferably carried out at 110 to 140 ° C.
  • the esterification is expediently carried out under inert conditions performed.
  • the procedure is advantageously such that the Condensed azeotropically in a heat exchanger and in a phase separation vessel into an upper organic phase and a lower water phase separates. Conducts through an appropriate pipeline the organic phase is returned to the esterification reactor.
  • esterification reactors distillers used, e.g. stirred tank reactors, Bubble distillers with and without circulation, thin-film evaporators, Falling film evaporator and tube bundle evaporator.
  • the course of the esterification can be followed by the one formed Amount of water, the acid number and / or the OH number of the reaction mixture is determined titrimetrically on samples.
  • the esterification is carried out until the amount of water is not increases more or the acid number or OH number no longer decreases.
  • the degree of alkoxylation of the alkyl polyalkylene glycol you need different times for this. The higher the The degree of alkoxylation is, the longer the esterification takes.
  • the organic solvent can be used after esterification remain in the esterification mixture. Usually included the mixtures 10 to 40 wt .-%, preferably 15 to 30 % By weight, organic solvent.
  • the esterification mixtures obtained usually contain in addition to the catalyst and inhibitors, the following monomers, which react in the subsequent radical polymerization can: acrylic acid, acrylic acid-alkyl polyalkylene glycol ester, polyalkylene glycol diacrylic acid ester in amounts below 5% by weight, preferably less than 3% by weight, and unesterified alkyl polyalkylene glycol in amounts below 10% by weight.
  • the liquid esterification mixtures obtained are at 10 to 100 ° C, especially at 30 to 60 ° C, storable for at least 8 weeks, without showing hydrolysis. They are easy to flow and pump and have viscosities of ⁇ 100 mPas at 40 ° C. For the subsequent polymerization they can be carried out without prior cleaning operation be used.
  • the esterification mixture undergoes radical polymerization in an aqueous medium, at the same time the organic solvent removed from the polymerization reactor by azeotropic distillation becomes.
  • polymerization initiator Peroxo and azo initiators are used.
  • Particularly preferred Polymerization initiators are hydrogen peroxide and Sodium, potassium and ammonium peroxodisulfate.
  • the amounts of initiator are usually 0.1 to 10% by weight, preferably 0.5 to 5 wt .-%, based on the monomers to be polymerized.
  • the molecular weight of the polymers can advantageously with the aid of Polymerization regulators can be specifically set to the presence however, polymerization regulators are not required.
  • Water-soluble ones are preferably used as polymerization regulators Sulfur, nitrogen and phosphorus compounds used.
  • examples for particularly suitable initiators are sodium hydrogen sulfite, Sodium disulfite, sodium sulfite, sodium thiosulfate, Sodium hypophosphite, phosphorous acid, mercaptopropionic acid, Mercaptoacetic acid, mercaptoethanol and alkali metal salts of the above Acids.
  • Mixtures of the above can of course also be used Polymerization regulators are used. If a polymerization regulator is used, the amounts used are in generally 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the monomers to be polymerized.
  • the polymerization can be continuous or discontinuous be performed.
  • it is advisable to place Water as a polymerization medium in a boiler before that with mixing device, reflux condenser and water separator equipped, it heats up to the polymerization temperature and gives continuously after starting the polymerization or batchwise the esterification mixture, initiator and if necessary regulators.
  • the polymerization can be carried out at normal pressure, under elevated pressure or can also be carried out under reduced pressure.
  • the polymerization always takes place while the reaction mixture is boiling.
  • the azeotrope is condensed as in the esterification reaction and separated in two phases.
  • the organic phase can be advantageous can be reused during esterification. Should be cleaning a liquid-liquid extraction may be necessary be done with water.
  • solvent can also be distilled or cleaned be subjected to steam distillation.
  • the monomers, the initiator and possibly the regulator to the reactor in FIG. 1 up to 20 h, especially in 2 to 10 h.
  • the reaction mixture is usually polymerized still 0.1 to 10 h, preferably 0.5 to 3 h after.
  • the postpolymerization is carried out with boiling of the reaction mixture by. If appropriate, residues of organic Distilled solvent from the polymerization mixture become.
  • the proportion of organic Solvent in the aqueous polymer solution preferably ⁇ 100 ppm. According to the method according to the invention, it is even possible the organic solvent completely from the at To remove polymerization mixture obtained, so that the residual contents of organic solvent from 0 to 50 ppm, mostly 1 up to 30 ppm.
  • a base can be added before, during or preferably after the polymerization. All basic reacting compounds can be used for this. Suitable are, for example, alkali metal oxides, hydroxides, carbonates and hydrogen carbonates, the potassium and especially the sodium compounds being preferred, alkaline earth metal oxides and hydroxides, in particular the magnesium, calcium and barium compounds, aluminum hydroxide, iron hydroxide, iron oxide, ammonia and amines such as cyclohexylamine, dicyclohexylamine, butylamine, ethanolamine, diethanolamine, triethanolamine and morpholine.
  • Sodium hydroxide in particular in the form of 10 to 50% by weight aqueous solutions, is preferably used for the neutralization.
  • the molecular weight M w of the polymers according to the invention is generally 1000 to 100,000, preferably 5000 to 50,000.
  • the polymers according to the invention are outstandingly suitable as Additive for cementitious systems, especially for mortar and concrete.
  • the amount of the polymers according to the invention used is usually 0.1 to 5 wt .-%, based on the cementitious system.
  • the polymers according to the invention have excellent effects as a plasticizer. They show the entire processing chain of concrete a constant liquefaction effect and can therefore be used to advantage in ready-mixed concrete. They can be used widely for different cement systems, regardless of their origin, manufacture, composition and aggregates such as sand, gravel and fine aggregates, as even at low and high temperatures, i.e. in winter and in Summer, and different water quality.
  • cementitious system as a powder, granulate, melt or as an aqueous solution (usually 30 to 60% by weight before, during or added after grinding.
  • the conversion in the esterification was determined by NMR spectroscopy.
  • the K value of the polymers was determined according to H. Fikentscher, Cellulose-Chemie, Volume 13, pages 58-64 and 71-74 (1932) in aqueous Solution at a pH of 7, a temperature of 25 ° C and a concentration of the sodium salt of the polymer of 1 Wt .-% determined.
  • a mixture of 500 g (0.5 mol) of methyl polyethylene glycol (M w 1000), 90 g (1.25 mol) of acrylic acid, 0.2 g of phenothiazine, 6 g of p-toluenesulfonic acid hydrate and 260 g of toluene were heated to 135 ° C. for 9 hours while passing nitrogen through (formation of 9 g of water).
  • the acid number of the storable esterification mixture which was liquid at 20 ° C. was 50 mg KOH / g.
  • Feed 1 400 g of ester 1; Feed 2: 53 g of an 8% by weight aqueous sodium peroxodisulfate solution; Feed 3: 27 g of a 10 wt .-% aqueous sodium bisulfite solution. Feed 1 was metered in in 6 h, inlets 2 and 3 each in 6.25 h.
  • the toluene was constantly azeotropic during the polymerization distilled off with water, which in the water separator into a water phase and a toluene phase was separated.
  • the water phase was returned to the polymerization reactor, which was toluene kept for reuse. After the end of the inflows 1 hour more water and residual toluene was distilled off.
  • the residual toluene content in the polymer solution was ⁇ 20 ppm.
  • Example 2 The procedure was analogous to Example 1, but the following were: Inlets used: Inlet 1: 400 g of ester 2; Feed 2: 53 g one 5 8% by weight aqueous sodium peroxodisulfate solution; Feed 3: 27 g a 12 wt .-% aqueous sodium bisulfite solution. A 35% by weight polymer solution with a pH of 7 was obtained. The K value of the polymer was 27.
  • Example 2 The procedure was analogous to Example 1, but the following were: Inlets used: Inlet 1: 350 g of ester 3; Inlet 2: 48 g of one 8% by weight aqueous sodium peroxodisulfate solution; Feed 3: 27 g 5 of a 40 wt .-% aqueous sodium bisulfite solution.
  • to Neutralization was carried out using 43 g of 50% strength by weight sodium hydroxide solution. A 35% by weight polymer solution with a pH of 6.9 was obtained. The K value of the polymer was 22.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Curing Cements, Concrete, And Artificial Stone (AREA)
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Abstract

Water-soluble polymers (I) of esters of acrylic acid (II) and alkyl-polyalkylene glycols (III) are obtained by a method involving azeotropic esterification of (II) and (III) in presence of organic solvent followed by radical polymerisation of the mixture with removal of solvent by azeotropic distillation and replacement of the lost water. <??>Water-soluble polymers (I) of esters of acrylic acid (II) and alkylpolyalkylene glycols (III), obtained by azeotropic esterification of a mixture of (II) and (III) in a mol ratio of (2-3):1 in presence of at least 85 wt% (based on III) of an organic solvent which forms an azeotrope with water, followed by radical polymerisation of the resulting mixture with azeotropic distillation to remove the solvent and with replacement of lost water by recycling or by the addition of fresh water. <??>An Independent claim is also included for a method for the production of (I) as described above.

Description

Die vorliegende Erfindung betrifft wasserlösliche Polymerisate von Estern aus Acrylsäure und Alkylpolyalkylenglykolen, welche erhältlich sind durch azeotrope Veresterung einer Mischung von Acrylsäure und Alkylpolyalkylenglykol im Molverhältnis von 2 bis 3 : 1 in Gegenwart eines organischen Lösungsmittels, das mit Wasser ein Azeotrop bildet, zu mindestens 85 Gew.-%, bezogen auf das Alkylpolyalkylenglykol, und anschließende radikalische Polymerisation des bei der Veresterung erhaltenen Gemisches in wäßrigem Medium, wobei man das organische Lösungsmittel während der Polymerisation azeotrop aus dem Reaktionsgemisch abdestilliert und das abdestillierte Wasser in das Gemisch zurückführt oder durch Zufuhr von frischem Wasser ersetzt.The present invention relates to water-soluble polymers of esters from acrylic acid and alkyl polyalkylene glycols, which are obtainable by azeotropic esterification of a mixture of Acrylic acid and alkyl polyalkylene glycol in a molar ratio of 2 to 3: 1 in the presence of an organic solvent mixed with water forms an azeotrope, at least 85 wt .-%, based on the Alkyl polyalkylene glycol, and subsequent radical polymerization of the mixture obtained in the esterification in aqueous Medium, using the organic solvent during the Polymerization distilled off azeotropically from the reaction mixture and the distilled water returns to the mixture or replaced with fresh water.

Außerdem betrifft die Erfindung die Herstellung der Polymerisate sowie ihre Verwendung als Zusatz zu zementösen Systemen, insbesondere als Verflüssiger und Mahlhilfsmittel.The invention also relates to the preparation of the polymers and their use as an additive to cementitious systems, in particular as a condenser and grinding aid.

Wasserlösliche Polymerisate auf Basis von Polycarbonsäure-Alkylpolyalkylenglykol-Estern sind aufgrund ihrer besonders guten Dispergierung von Zement in wäßrigen Suspensionen von zunehmendem technischen Interesse für die Bauindustrie, wo sie als Betonverflüssiger eingesetzt werden. Sie lösen dabei die bisherigen Betonverflüssiger auf Basis von Melamin- oder Naphthalin-Formaldehyd-Sulfonaten ab, da sie eine bedeutend höhere Dispergierfähigkeit besitzen.Water-soluble polymers based on polycarboxylic acid alkyl polyalkylene glycol esters are due to their particularly good Dispersion of cement in aqueous suspensions of increasing technical interest in the construction industry, where it acts as a plasticizer be used. You solve the previous ones Concrete plasticizer based on melamine or naphthalene-formaldehyde sulfonates as it has a significantly higher dispersibility have.

Bei den bislang bekannten Polycarbonsäure-Alkylpolyethylenglykol-Estern besteht noch der Nachteil, daß sie im Verlauf der Anwendung als Betonverflüssiger an Wirksamkeit verlieren und die Fließfähigkeit von Beton schlechter wird. Dies ist besonders bei Transportbeton problematisch, bei dem die Fließfähigkeit im Mischwerk eingestellt wird. Der Beton sollte bei der Verarbeitung auf der Baustelle noch dieselben Fließeigenschaften haben. Deshalb wird heute noch vielfach Verflüssiger auf der Baustelle nachdosiert, was zu schwankender Qualität des Betons führen kann.In the polycarboxylic acid alkyl polyethylene glycol esters known to date there is still the disadvantage that they are in the course of application as a plasticizer lose effectiveness and the Flowability of concrete deteriorates. This is particularly the case with Ready-mixed concrete problematic, where the flowability in the mixing plant is set. The concrete should be used during processing still have the same flow properties on the construction site. Therefore is still used many times as a condenser on the construction site replenishes, which can lead to fluctuating quality of the concrete.

Aus der EP-A-989 108 sind Dispergiermittel für Beton auf Basis polymerer Ester von Acrylsäure und Methylpolyethylenglykol bekannt, die durch azeotrope Veresterung von Acrylsäure und Methylpolyethylenglykol (Mw 472) im Molverhältnis 3,35 : 1 in Cyclohexan, anschließenden Ersatz des Cyclohexans durch zugesetztes Wasser mittels azeotroper Destillation und Polymersiation der erhaltenen 80 gew.-%igen wäßrigen Esterlösung in Wasser hergestellt werden. Es handelt sich hierbei um einen dreistufigen Herstellungsprozeß, bei dem im Destillationsschritt auch Probleme mit der Verunreinigung der Apparatur durch mitabdestillierte Acrylsäure auftreten, weshalb die Zuführung eines Polymerisationsinhibitors in den Kühler erforderlich ist. Außerdem zeigen die auf diese Weise erhaltenen Verbindungen nichtzufriedenstellende Anwendungseigenschaften.EP-A-989 108 discloses dispersants for concrete based on polymeric esters of acrylic acid and methylpolyethylene glycol, which are obtained by azeotropic esterification of acrylic acid and methylpolyethylene glycol (M w 472) in a molar ratio of 3.35: 1 in cyclohexane, followed by replacement of the cyclohexane by added water can be prepared by azeotropic distillation and polymerization of the resulting 80 wt .-% aqueous ester solution in water. This is a three-stage manufacturing process in which problems with the contamination of the apparatus by co-distilled acrylic acid also occur in the distillation step, which is why the addition of a polymerization inhibitor to the cooler is necessary. In addition, the compounds thus obtained show unsatisfactory application properties.

In der älteren deutschen Patentanmeldung 199 57 177.5 werden Dispergiermittel auf Basis polymerer Ester von Methacrylsäure und Methylpolyethylenglykol beschrieben.In the older German patent application 199 57 177.5 Dispersant based on polymeric esters of methacrylic acid and Methyl polyethylene glycol described.

Der Erfindung lag die Aufgabe zugrunde, Betonverflüssiger bereitzustellen, die sich durch vorteilhafte Anwendungseigenschaften auszeichnen, insbesondere über die gesamte Verarbeitungskette von Transportbeton, also während der Herstellungs-, Transport- und Verarbeitungsdauer, eine gleichbleibende Verflüssigungswirkung aufweisen, und auf wirtschaftliche Weise herzustellen sind.The object of the invention was to provide concrete plasticizers, which is characterized by advantageous application properties distinguish, in particular across the entire processing chain of Ready-mix concrete, i.e. during manufacturing, transportation and Processing time, a constant liquefaction effect have, and are economical to produce.

Demgemäß wurden die eingangs definierten wasserlöslichen Polymerisate von Estern aus Acrylsäure und Alkylpolyalkylenglykolen gefunden.Accordingly, the water-soluble polymers defined at the outset of esters from acrylic acid and alkyl polyalkylene glycols found.

Weiterhin wurde das hierdurch definierte Verfahren zur Herstellung der Polymerisate gefunden.Furthermore, the method of manufacture defined hereby of the polymers found.

Nicht zuletzt wurde die Verwendung der Polymerisate als Zusatz zu zementösen Systemen gefunden.Last but not least, the use of the polymers as an additive became too cementitious systems found.

Zur Herstellung der erfindungsgemäßen Polymerisate wird ein Gemisch von Acrylsäure und Alkylpolyalkylenglykol im Molverhältnis 2 bis 3 : 1, bevorzugt von 2,2 bis 3 : 1 und besonders bevorzugt von 2,5 bis 3 : 1 eingesetzt, das einer vorzugsweise sauer katalysierten, azeotropen Veresterung unterworfen wird. Die überschüssige, nicht mit dem Alkylpolyalkylenglykol reagierende Acrylsäure verbleibt in der bei der Veresterung erhaltenen Mischung und reagiert als Comonomer bei der anschließenden radikalischen Polymerisation.To produce the polymers according to the invention, a Mixture of acrylic acid and alkyl polyalkylene glycol in a molar ratio 2 to 3: 1, preferably from 2.2 to 3: 1 and particularly preferably used from 2.5 to 3: 1, one preferably acid-catalyzed, azeotropic esterification is subjected. The excess that does not react with the alkyl polyalkylene glycol Acrylic acid remains in the one obtained during the esterification Mixture and reacts as a comonomer in the subsequent radical polymerization.

Manchmal kann es von Vorteil sein, wenn zur Veresterung zusätzlich zu der Acrylsäure bis zu 0,5 mol einer weiteren monoethylenisch ungesättigten Carbonsäure, bzw. einem Carbonsäurederivat wie Maleinsäure, Maleinsäureanhydrid oder Fumarsäure, eingesetzt werden. Bevorzugt wird die Veresterung jedoch in Abwesenheit dieser Säuren vorgenommen. Sometimes it can be beneficial to add to the esterification to acrylic acid up to 0.5 mol of another monoethylenic unsaturated carboxylic acid, or a carboxylic acid derivative such as maleic acid, maleic anhydride or fumaric acid, be used. However, the esterification is preferred in the absence of these acids.

Die azeotrope Veresterung der Acrylsäure mit dem Alkylpolyalkylenglykol erfolgt in Gegenwart eines organischen Lösungsmittels, das mit Wasser ein Azeotrop bildet, und kann nach an sich bekannten Verfahren vorgenommen werden. Das organische Lösungsmittel wird dabei auch als Schleppmittel bezeichnet. Bei der azeotropen Veresterung wird das bei der Reaktion entstehende Wasser azeotrop aus dem Reaktionsgemisch entfernt.The azeotropic esterification of acrylic acid with the alkyl polyalkylene glycol takes place in the presence of an organic solvent, that forms an azeotrope with water, and can be according to known Procedures are made. The organic solvent is also referred to as an entrainer. With the azeotropic Esterification causes the water formed during the reaction to become azeotropic removed from the reaction mixture.

Die Veresterung wird mindestens soweit geführt, bis ein Umsatz von 85 Gew.-%, vorzugsweise mindestens 90 Gew.-%, bezogen auf das Alkylpolyalkylenglykol, erreicht ist. Der Umsatz kann dabei anhand der Abnahme der Säurezahl (Acrylsäure) oder der OH-Zahl (A1-kylpolyalkylenglykol) des Reaktionsgemisches verfolgt werden. Außerdem besteht nach der Polymerisation die Möglichkeit, mit Hilfe von Gelpermeationschromatographie-Untersuchungen (GPC) den unveresterten Anteil an Alkylpolyalkylenglykol neben dem Polymer zu ermitteln.The esterification is carried out at least until sales of 85% by weight, preferably at least 90% by weight, based on the Alkyl polyalkylene glycol, is reached. The turnover can be based on decrease in acid number (acrylic acid) or OH number (A1-kylpolyalkylenglykol) of the reaction mixture are followed. Moreover after polymerization there is the possibility of using of gel permeation chromatography tests (GPC) the unesterified Proportion of alkyl polyalkylene glycol in addition to the polymer determine.

Als veresterndes Alkylpolyalkylenglykol eignen sich erfindungsgemäß insbesondere Verbindungen der allgemeinen Formeln R1-(O-CHR2-CHR3)n-OH   und   R1-(O-CH2-CH2-CH2-CH2)n-OH in denen die Variablen folgende Bedeutung haben:

R1
C1-C50-Alkyl, bevorzugt C1-C4-Alkyl, oder C1-C18-Alkylphenyl;
R2, R3
unabhängig voneinander Wasserstoff, Methyl oder Ethyl;
n
5 bis 90.
According to the invention, compounds of the general formulas are particularly suitable as esterifying alkyl polyalkylene glycol R 1 - (O-CHR 2 -CHR 3 ) n -OH and R 1 - (O-CH 2 -CH 2 -CH 2 -CH 2 ) n -OH in which the variables have the following meaning:
R 1
C 1 -C 50 alkyl, preferably C 1 -C 4 alkyl, or C 1 -C 18 alkylphenyl;
R 2 , R 3
independently of one another hydrogen, methyl or ethyl;
n
5 to 90.

Das Molgewicht Mw der Alkylpolyalkylenglykole beträgt in der Regel 350 bis 4000, bevorzugt 500 bis 2000, besonders bevorzugt 750 bis 1500 und ganz besonders bevorzugt etwa 1000.The molecular weight M w of the alkyl polyalkylene glycols is generally 350 to 4000, preferably 500 to 2000, particularly preferably 750 to 1500 and very particularly preferably approximately 1000.

Besonders bevorzugt werden Alkylpolyethylenglykole und ganz besonders bevorzugt Methylpolyethylenglykole der genannten Molgewichte eingesetzt.Alkyl polyethylene glycols are particularly preferred and very particularly preferably methyl polyethylene glycols of the molecular weights mentioned used.

Weiterhin sind als Alkylpolyalkylenglykol auch Alkyl- (insbesondere Methyl)-polyalkylenglykole geeignet, die Einheiten von Propylenoxid und/oder Butylenoxid in Kombination mit Einheiten von Ethylenoxid enthalten. Gleiche Einheiten können dabei blockweise oder statistisch angeordnet sein. Furthermore, alkyl (especially Methyl) polyalkylene glycols suitable, the units of Propylene oxide and / or butylene oxide in combination with units of ethylene oxide. The same units can be used in blocks or be statistically arranged.

Beispiele hierfür sind Methylpolyalkylenglykole, die durch Anlagerung von Ethylenoxid und Propylenoxid an einwertige aliphatische Alkohole, insbesondere durch Anlagerung von

  • 5 mol Ethylenoxid und 1 mol Propylenoxid,
  • 5 mol Ethylenoxid und 3 mol Propylenoxid,
  • 5 mol Ethylenoxid und 10 mol Propylenoxid,
  • 10 mol Ethylenoxid und 1 mol Propylenoxid,
  • 10 mol Ethylenoxid und 3 mol Propylenoxid,
  • 10 mol Ethylenoxid und 10 mol Propylenoxid,
  • 20 mol Ethylenoxid und 1 mol Propylenoxid,
  • 20 mol Ethylenoxid und 3 mol Propylenoxid,
  • 20 mol Ethylenoxid und 10 mol Propylenoxid,
  • 25 mol Ethylenoxid und 1 mol Propylenoxid,
  • 25 mol Ethylenoxid und 3 mol Propylenoxid bzw.
  • 25 mol Ethylenoxid und 10 mol Propylenoxid
    • an 1 mol Methanol, Ethanol, n-Propanol, Isopropanol oder Butanol erhältlich sind.Examples of these are methyl polyalkylene glycols, which are formed by the addition of ethylene oxide and propylene oxide to monohydric aliphatic alcohols, in particular by the addition of
  • 5 moles of ethylene oxide and 1 mole of propylene oxide,
  • 5 moles of ethylene oxide and 3 moles of propylene oxide,
  • 5 moles of ethylene oxide and 10 moles of propylene oxide,
  • 10 moles of ethylene oxide and 1 mole of propylene oxide,
  • 10 moles of ethylene oxide and 3 moles of propylene oxide,
  • 10 moles of ethylene oxide and 10 moles of propylene oxide,
  • 20 moles of ethylene oxide and 1 mole of propylene oxide,
  • 20 moles of ethylene oxide and 3 moles of propylene oxide,
  • 20 moles of ethylene oxide and 10 moles of propylene oxide,
  • 25 mol ethylene oxide and 1 mol propylene oxide,
  • 25 mol ethylene oxide and 3 mol propylene oxide or
  • 25 moles of ethylene oxide and 10 moles of propylene oxide
    • 1 mol of methanol, ethanol, n-propanol, isopropanol or butanol are available.

    Es kann auch teilverethertes Polytetrahydrofuran eingesetzt werden, das einseitig als Endgruppe eine Alkylgruppe, vorzugsweise eine C1-C4-Alkylgruppe, trägt.It is also possible to use partially etherified polytetrahydrofuran which, on one side, carries an alkyl group, preferably a C 1 -C 4 alkyl group, as the end group.

    Die Wirksamkeit der Copolymerisate im jeweiligen zementösen System läßt sich manchmal erhöhen, wenn Mischungen aus Alkylpolyalkylenglykolen mit unterschiedlichen Molgewichten eingesetzt werden.The effectiveness of the copolymers in the respective cementitious system can sometimes be increased if mixtures of alkyl polyalkylene glycols can be used with different molecular weights.

    Geeignete Mischungen haben beispielsweise folgende Zusammensetzungen:

  • 30 Gew.-% Methylpolyethylenglykol (Mw 350) und 70 Gew.-% Methylpolyethylenglykol (Mw 1000),
  • 50 Gew.-% Methylpolyethylenglykol (Mw 350) und 50 Gew.-% Methylpolyethylenglykol (Mw 2000),
  • 70 Gew.-% Methylpolyethylenglykol (Mw 350) und 30 Gew.-% Methylpolyethylenglykol (Mw 4000),
  • 30 Gew.-% Methylpolyethylenglykol (Mw 500) und 70 Gew.-% Methylpolyethylenglykol (Mw 1000),
  • 30 Gew.-% Methylpolyethylenglykol (Mw 500) und 70 Gew.-% Methylpolyethylenglykol (Mw 2000),
  • 30 Gew.-% Methylpolyethylenglykol (Mw 750) und 70 Gew.-% Methylpolyethylenglykol (Mw 1000),
  • 30 Gew.-% Methylpolyethylenglykol (Mw 750) und 70 Gew.-% Methylpolyethylenglykol (Mw 2000),
  • 50 Gew.-% Methylpolyethylenglykol (Mw 1000) und 50 Gew.-% Methylpolyethylenglykol (Mw 2000),
  • 90 Gew.-% Methylpolyethylenglykol (Mw 1000) und 10 Gew.-% Methylpolyethylenglykol (Mw 4000),
  • 90 Gew.-% Methylpolyethylenglykol (Mw 1000) und 10 Gew.-% Methylpolypropylenglykol (Mw 1350),
  • 90 Gew.-% Methylpolyethylenglykol (Mw 1000) und 10 Gew.-% Methylpolypropylenglykol (Mw 2000) und
  • 90 Gew.-% Methylpolyethylenglykol (Mw 1000) und 10 Gew.-% Methylpolyethylenglykol/Methylpropylenglykol-Copolymer im Molverhältnis 90:10 (Mw 1000).
    • Suitable mixtures have, for example, the following compositions:
  • 30% by weight of methyl polyethylene glycol (M w 350) and 70% by weight of methyl polyethylene glycol (M w 1000),
  • 50% by weight of methyl polyethylene glycol (M w 350) and 50% by weight of methyl polyethylene glycol (M w 2000),
  • 70% by weight of methyl polyethylene glycol (M w 350) and 30% by weight of methyl polyethylene glycol (M w 4000),
  • 30% by weight of methyl polyethylene glycol (M w 500) and 70% by weight of methyl polyethylene glycol (M w 1000),
  • 30% by weight of methyl polyethylene glycol (M w 500) and 70% by weight of methyl polyethylene glycol (M w 2000),
  • 30% by weight of methyl polyethylene glycol (M w 750) and 70% by weight of methyl polyethylene glycol (M w 1000),
  • 30% by weight of methyl polyethylene glycol (M w 750) and 70% by weight of methyl polyethylene glycol (M w 2000),
  • 50% by weight of methyl polyethylene glycol (M w 1000) and 50% by weight of methyl polyethylene glycol (M w 2000),
  • 90% by weight of methyl polyethylene glycol (M w 1000) and 10% by weight of methyl polyethylene glycol (M w 4000),
  • 90% by weight of methyl polyethylene glycol (M w 1000) and 10% by weight of methyl polypropylene glycol (M w 1350),
  • 90% by weight of methyl polyethylene glycol (M w 1000) and 10% by weight of methyl polypropylene glycol (M w 2000) and
  • 90% by weight of methyl polyethylene glycol (M w 1000) and 10% by weight of methyl polyethylene glycol / methyl propylene glycol copolymer in a molar ratio of 90:10 (M w 1000).

    • Zweckmäßigerweise wird die Veresterung in Gegenwart eines Katalysators vorgenommen. Als Katalysator können dabei alle organischen und anorganischen Säuren eingesetzt werden. Beispiele für geeignete saure Katalysatoren sind Schwefelsäure, schweflige Säure, Di- und Polyschwefelsäure, Schwefeltrioxid, Methansulfonsäure, Benzolsulfonsäure, p-Toluolsulfonsäure, C2-C30-Alkylbenzolsulfonsäuren, Schwefelsäuremonoester von C1-C30-Alkoholen und Alkylpolyalkylenglykolen, Phosphorsäure, phosphorige Säure, unterphosphorige Säure, Polyphosphorsäure, Salzsäure, Perchlorsäure und saure Ionenaustauscher. Bevorzugt sind p-Toluolsulfonsäure und Methansulfonsäure, besonders bevorzugt ist p-Toluolsulfonsäure.The esterification is expediently carried out in the presence of a catalyst. All organic and inorganic acids can be used as catalysts. Examples of suitable acidic catalysts are sulfuric acid, sulfurous acid, di- and polysulfuric acid, sulfur trioxide, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, C 2 -C 30 alkylbenzenesulfonic acids, sulfuric acid monoesters of C 1 -C 30 alcohols and alkylpolyalkylene glycolic acid, phosphoric acid , hypophosphorous acid, polyphosphoric acid, hydrochloric acid, perchloric acid and acidic ion exchangers. P-Toluenesulfonic acid and methanesulfonic acid are preferred, p-toluenesulfonic acid is particularly preferred.

    Die Menge an Katalysator, bezogen auf die Summe aus Acrylsäure und Alkylpolyalkylenglykol, beträgt im allgemeinen bis zu 10 Gew.-%, bevorzugt 0,05 bis 7 Gew.-% und besonders bevorzugt 0,1 bis 5 Gew.-%.The amount of catalyst based on the total of acrylic acid and alkyl polyalkylene glycol is generally up to 10 % By weight, preferably 0.05 to 7% by weight and particularly preferably 0.1 up to 5% by weight.

    Als Schleppmittel bei der Veresterung geeignete organische Lösungsmittel sind aliphatische (isoaliphatische und linearaliphatische), cycloaliphatische, aliphatisch-aromatische und rein aromatische Kohlenwasserstoffe. Der Siedepunkt besonders geeigneter organischer Lösungsmittel liegt in der Regel bei 60 bis 300°C, vorzugsweise bei 70 bis 150°C.Suitable organic entrainer during esterification Solvents are aliphatic (isoaliphatic and linear aliphatic), cycloaliphatic, aliphatic-aromatic and pure aromatic hydrocarbons. The boiling point is particularly suitable organic solvent is usually 60 to 300 ° C, preferably at 70 to 150 ° C.

    Beispiele für geeignete organische Lösungsmittel sind im einzelnen:

  • n-Paraffine wie Hexan, Decan, Undecan, Dodecan und Octadecan; Isoparaffine wie Isooctan, Isodecan, Isododecan, Isohexadecan und
    Isooctadecan;
    Cycloparaffine wie Cyclohexan, Methylcyclohexan und Dimethylcyclohexan;
    • Examples of suitable organic solvents are:
  • n-paraffins such as hexane, decane, undecane, dodecane and octadecane; Isoparaffins such as isooctane, isodecane, isododecane, isohexadecane and
    Isooctadecan;
    Cycloparaffins such as cyclohexane, methylcyclohexane and dimethylcyclohexane;

    • Aromaten wie Benzol, Toluol, o-, m- und p-Xylol, Xylolgemische, Trimethylbenzol, Tetramethylbenzol, Mesitylen, Ethylbenzol, Isopropylbenzol, n-Butylbenzol und Isobutylbenzol.Aromatics such as benzene, toluene, o-, m- and p-xylene, xylene mixtures, Trimethylbenzene, tetramethylbenzene, mesitylene, ethylbenzene, isopropylbenzene, n-butylbenzene and isobutylbenzene.

    Bevorzugt sind dabei Cyclohexan, Methylcyclohexan, Toluol, Xylolgemische und o-Xylol, wobei Toluol besonders bevorzugt ist.Cyclohexane, methylcyclohexane, toluene and xylene mixtures are preferred and o-xylene, with toluene being particularly preferred.

    Es können auch technisch verfügbare, einen Siedebereich aufweisende Mischungen aus verschiedenen organischen Lösungsmitteln verwendet werden. Solche Mischungen werden auch als Spezialbenzine, Petroleumbenzine, Siedegrenzenbenzine, Naphtha und Petroletherfraktionen bezeichnet. Sie fallen oft als Raffineriefraktionen an und können durch Oligomerisierungen und Hydrierungen gezielt aus Steamcracker-Olefinen hergestellt werden. Beispiele für solche Siedegrenzenbenzine sind Benzine mit Siedebereichen von 90 bis 100°C, 100 bis 140°C und 140 bis 160°C. Die Fraktionen können je nach Herkunft rein linearaliphatisch, rein isoaliphatische, rein aliphatisch-aromatische oder rein aromatische Bestandteile enthalten.There can also be technically available boiling ranges Mixtures of different organic solvents be used. Such mixtures are also known as special gasoline, Petroleum spirit, boiling-point spirit, naphtha and petroleum ether fractions designated. They often fall as refinery fractions and can be targeted by oligomerizations and hydrogenations be made from steam cracker olefins. examples for Such boiling-point petrol is a gasoline with a boiling range of 90 up to 100 ° C, 100 to 140 ° C and 140 to 160 ° C. The groups can depending on origin, purely linear aliphatic, purely isoaliphatic, purely aliphatic-aromatic or purely aromatic constituents contain.

    Übersichten zu den technisch zugänglichen Kohlenwasserstoffgemischen sind zu finden in: Kirk-Othmer, Encyclopedia of Chemical Technology, 1995, Vol. 13, Seiten 744 ff, Kapitel Hydrocarbons, und Vol. 12, Seiten 126 ff, Kapitel Fuels, sowie Seiten 341 ff, Kapitel Gasoline; Ullmann's Encyclopedia of Industrial Chemistry, 1989, Vol. A13, Seiten 227-281, im Kapitel Hydrocarbons, und Vol. A16, Seiten 719-755, im Kapitel Motor Fuels.Overviews of the technically accessible hydrocarbon mixtures can be found in: Kirk-Othmer, Encyclopedia of Chemical Technology, 1995, vol. 13, pages 744 ff, chapter hydrocarbons, and Vol. 12, pages 126 ff, chapter Fuels, and pages 341 ff, Chapter Gasoline; Ullmann's Encyclopedia of Industrial Chemistry, 1989, vol. A13, pages 227-281, in the chapter on hydrocarbons, and vol. A16, pages 719-755, in chapter Motor Fuels.

    Das Schleppmittel bildet zusammen mit Wasser ein azeotropes Gemisch, das in der Regel einen Siedepunkt unter dem des niedriger siedenden Bestandteils aufweist. Die Siedepunkte der azeotropen Gemische liegen bevorzugt im Bereich von 70 bis 130°C.The entrainer forms an azeotropic together with water Mixture that is usually a boiling point below that of the lower boiling component. The boiling points of the Azeotropic mixtures are preferably in the range from 70 to 130 ° C.

    Der Anteil an Schleppmittel in der Reaktionmischung beträgt üblicherweise 5 bis 50 Gew.-%, bevorzugt 10 bis 40 Gew.-%, bezogen auf die Summe aus Acrylsäure und Alkylpolyalkylenglykol. Die Menge an Schleppmittel wird dabei erfindungsgemäß vorteilhaft so gewählt, daß das Schleppmittel in der Reaktionsmischung einen Siedepunkt von 100 bis 150°C, vorzugsweise 110 bis 140°C, besitzt. Die Siedepunkte der Azeotrope und der Schleppmittel sind in der bei der Veresterung vorliegenden Mischung meist höher als die der reinen Substanzen.The proportion of entrainer in the reaction mixture is usually 5 to 50% by weight, preferably 10 to 40% by weight, based on the sum of acrylic acid and alkyl polyalkylene glycol. The amount of entrainer is advantageous according to the invention chosen so that the entrainer in the reaction mixture Boiling point of 100 to 150 ° C, preferably 110 to 140 ° C, has. The boiling points of the azeotropes and the entrainer are in the the mixture present in the esterification is usually higher than that of the pure substances.

    Um das einseitig endgruppenverschlossene Alkylpolyalkylenglykol während der Veresterung vor oxidativem Abbau zu schützen, können gewünschtenfalls Reduktionsmittel zugesetzt werden. Geeignete Reduktionsmittel sind z.B. Phosphorverbindungen wie hypophosphorige Säure und phosphorige Säure und Schwefelverbindungen wie Schwefeldioxid, Thiosulfat und Dithionit. Selbstverständlich können auch Reduktionsmittelmischungen zum Einsatz kommen.The alkyl polyalkylene glycol, which is end-capped at one end can protect against oxidative degradation during the esterification if desired, reducing agents are added. Suitable reducing agents are e.g. Phosphorus compounds such as hypophosphorous Acid and phosphorous acid and sulfur compounds such as Sulfur dioxide, thiosulfate and dithionite. Of course you can reducing agent mixtures are also used.

    Wenn Reduktionsmittel eingesetzt wird, dann beträgt die Menge im allgemeinen bis zu 5 Gew.-%, bevorzugt bis 2 Gew.-%, bezogen auf Alkylpolyalkylenglykol.If reducing agent is used, the amount is in generally up to 5% by weight, preferably up to 2% by weight, based on Alkylpolyalkylene.

    Um eine vorzeitige Polymerisation der Acrylsäure und der Acrylsäureester zu verhindern, werden dem bei der Veresterung eingesetzten Gemisch vorteilhaft übliche Polymerisationsinhibitoren wie Phenothiazin, Hydrochinonmonomethylether oder Di-tert.-butylp-kresol zugesetzt.To premature polymerization of acrylic acid and acrylic acid esters to prevent the used in the esterification Mixture advantageous conventional polymerization inhibitors such as phenothiazine, hydroquinone monomethyl ether or di-tert-butylp-cresol added.

    In der Regel liegt die Inhibitormenge bei 0,001 bis 2 Gew.-%, vorzugsweise bei 0,005 bis 0,5 Gew.-%, bezogen auf die Acrylsäure.As a rule, the amount of inhibitor is 0.001 to 2% by weight, preferably 0.005 to 0.5% by weight, based on the acrylic acid.

    Die Veresterung wird üblicherweise bei 80 bis 200°C, bevorzugt bei 90 bis 170°C und besonders bevorzugt bei 110 bis 140°C durchgeführt.The esterification is usually at 80 to 200 ° C, preferably at 90 to 170 ° C and particularly preferably carried out at 110 to 140 ° C.

    Zweckmäßigerweise wird die Veresterung unter inerten Bedingungen vorgenommen. Vorteilhaft leitet man während der Veresterung einen Stickstoffstrom durch die Reaktionsmischung, wodurch das Abdestillieren des Azeotrops unterstützt wird. Bevorzugt leitet man pro h das 0,1 bis 5-fache, insbesondere das 0,5 bis 2-fache Volumen des Reaktorinhalts an Stickstoff durch die Reaktionsmischung.The esterification is expediently carried out under inert conditions performed. One advantageously leads one during the esterification Nitrogen flow through the reaction mixture, causing the distillation of the azeotrope is supported. You prefer to lead 0.1 to 5 times, in particular 0.5 to 2 times, the volume per hour the reactor contents of nitrogen by the reaction mixture.

    Verfahrenstechnisch geht man vorteilhaft so vor, daß man das Azeotrop in einem Wärmetauscher kondensiert und in einem Phasentrenngefäß in eine obere organische Phase und eine untere Wasserphase trennt. Durch eine entsprechende Rohrleitungsführung leitet man die organische Phase wieder in den Veresterungsreaktor zurück. Als Veresterungsreaktor eignen sich dabei alle üblicherweise verwendeten Destillationsapparate, z.B. Rührkesselreaktoren, Blasendestillationsapparate mit und ohne Umwälzkreis, Dünnschichtverdampfer, Fallfilmverdampfer und Rohrbündelverdampfer.In terms of process engineering, the procedure is advantageously such that the Condensed azeotropically in a heat exchanger and in a phase separation vessel into an upper organic phase and a lower water phase separates. Conducts through an appropriate pipeline the organic phase is returned to the esterification reactor. All are usually suitable as esterification reactors distillers used, e.g. stirred tank reactors, Bubble distillers with and without circulation, thin-film evaporators, Falling film evaporator and tube bundle evaporator.

    Der Verlauf der Veresterung kann verfolgt werden, indem die gebildete Menge Wasser, die Säurezahl und/oder die OH-Zahl des Reaktionsgemisches an Proben titrimetrisch ermittelt wird.The course of the esterification can be followed by the one formed Amount of water, the acid number and / or the OH number of the reaction mixture is determined titrimetrically on samples.

    Die Veresterung wird so weit geführt, bis die Wassermenge nicht mehr zunimmt bzw. die Säurezahl oder OH-Zahl nicht mehr abnimmt. In Abhängigkeit vom Alkoxylierungsgrad des Alkylpolyalkylenglykols benötigt man hierfür unterschiedliche Zeiten. Je höher der Alkoxylierungsgrad ist, um so länger dauert die Veresterung.The esterification is carried out until the amount of water is not increases more or the acid number or OH number no longer decreases. Depending on the degree of alkoxylation of the alkyl polyalkylene glycol you need different times for this. The higher the The degree of alkoxylation is, the longer the esterification takes.

    Das organische Lösungsmittel kann nach abgeschlossener Veresterung in der Veresterungsmischung verbleiben. Üblicherweise enthalten die Mischungen 10 bis 40 Gew.-%, vorzugsweise 15 bis 30 Gew.-%, organisches Lösungsmittel.The organic solvent can be used after esterification remain in the esterification mixture. Usually included the mixtures 10 to 40 wt .-%, preferably 15 to 30 % By weight, organic solvent.

    Die erhaltenen Veresterungsmischungen enthalten üblicherweise weiterhin neben Katalysator und Inhibitoren folgende Monomere, die bei der anschließenden radikalischen Polymerisation reagieren können: Acrylsäure, Acrylsäure-Alkylpolyalkylenglykol-Ester, Polyalkylenglykoldiacrylsäure-Ester in Mengen unter 5 Gew.-%, bevorzugt unter 3 Gew.-%, und unverestertes Alkylpolyalkylengkylol in Mengen unter 10 Gew.-%.The esterification mixtures obtained usually contain in addition to the catalyst and inhibitors, the following monomers, which react in the subsequent radical polymerization can: acrylic acid, acrylic acid-alkyl polyalkylene glycol ester, polyalkylene glycol diacrylic acid ester in amounts below 5% by weight, preferably less than 3% by weight, and unesterified alkyl polyalkylene glycol in amounts below 10% by weight.

    Die erhaltenen flüssigen Veresterungsmischungen sind bei 10 bis 100°C, insbesondere bei 30 bis 60°C, mindestens 8 Wochen lagerfähig, ohne Hydrolyse zu zeigen. Sie sind gut fließfähig und pumpbar und weisen bei 40°C Viskositäten < 100 mPas auf. Für die anschließende Polymerisation können sie ohne vorherige Reinigungsoperation eingesetzt werden.The liquid esterification mixtures obtained are at 10 to 100 ° C, especially at 30 to 60 ° C, storable for at least 8 weeks, without showing hydrolysis. They are easy to flow and pump and have viscosities of <100 mPas at 40 ° C. For the subsequent polymerization they can be carried out without prior cleaning operation be used.

    Die radikalische Polymerisation der Veresterungsmischung erfolgt in wäßrigem Medium, wobei gleichzeitig das organische Lösemittel durch azeotrope Destillation aus dem Polymerisationsreaktor entfernt wird.The esterification mixture undergoes radical polymerization in an aqueous medium, at the same time the organic solvent removed from the polymerization reactor by azeotropic distillation becomes.

    Im Gegensatz zu dem in der EP-A-989 108 beschriebenen Polymerisationsverfahren ist beim erfindungsgemäßen Verfahren während der gesamten Polymerisation immer organisches Lösungsmittel in kleinen Mengen anwesend und beeinflußt damit die Löslichkeit und das Polymerisationsverhalten der Monomeren positiv. Die Mengen an organischem Lösungsmittel sind annähernd konstant, da das organische Lösungsmittel ständig durch das Veresterungsprodukt in den Polymerisationsreaktor eingetragen wird und gleichzeitig durch azeotrope Destillation ständig aus dem Reaktor entfernt wird. Es bildet sich somit während der Polymerisation eine Gleichgewichtskonzentration an organischem Lösungsmittel von etwa 0,01 bis 5 Gew.-%, bezogen auf das wäßrige Polymerisatlösung, aus.In contrast to the polymerization process described in EP-A-989 108 is in the inventive method during the throughout the polymerization always organic solvent in small Amounts present and thus affect the solubility and that Polymerization behavior of the monomers positive. The amounts of organic Solvents are almost constant because of that organic solvents constantly through the esterification product in the polymerization reactor is entered and at the same time constantly removed from the reactor by azeotropic distillation becomes. A thus forms during the polymerization Equilibrium organic solvent concentration of about 0.01 to 5% by weight, based on the aqueous polymer solution, out.

    Als Polymerisationsinitiator können alle bekannten wasserlöslichen Peroxo- und Azoinitiatoren eingesetzt werden. Besonders bevorzugte Polymerisationsinitiatoren sind Wasserstoffperoxid und Natrium-, Kalium- und Ammoniumperoxodisulfat. Die Mengen an Initiator betragen üblicherweise 0,1 bis 10 Gew.-%, vorzugsweise 0,5 bis 5 Gew.-%, bezogen auf die zu polymerisierenden Monomeren.All known water-soluble ones can be used as the polymerization initiator Peroxo and azo initiators are used. Particularly preferred Polymerization initiators are hydrogen peroxide and Sodium, potassium and ammonium peroxodisulfate. The amounts of initiator are usually 0.1 to 10% by weight, preferably 0.5 to 5 wt .-%, based on the monomers to be polymerized.

    Das Molgewicht der Polymerisate kann vorteilhaft mit Hilfe von Polymerisationsreglern gezielt eingestellt werden, die Anwesenheit von Polymerisationsreglern ist jedoch nicht erforderlich. Als Polymerisationsregler werden vorzugsweise wasserlösliche Schwefel-, Stickstoff- und Phosphorverbindungen verwendet. Beispiele für besonders geeignete Initiatoren sind Natriumhydrogensulfit, Natriumdisulfit, Natriumsulfit, Natriumthiosulfat, Natriumhypophosphit, phosphorige Säure, Mercaptopropionsäure, Mercaptoessigsäure, Mercaptoethanol und Alkalimetallsalze der genannten Säuren. Selbstverständlich können auch Mischungen der genannten Polymerisationsregler verwendet werden. Wenn ein Polymerisationsregler eingesetzt wird, liegen die verwendeten Mengen in der Regel bei 0,1 bis 10 Gew.-%, bevorzugt bei 1 bis 5 Gew.-%, bezogen auf die zu polymerisierenden Monomere.The molecular weight of the polymers can advantageously with the aid of Polymerization regulators can be specifically set to the presence however, polymerization regulators are not required. Water-soluble ones are preferably used as polymerization regulators Sulfur, nitrogen and phosphorus compounds used. Examples for particularly suitable initiators are sodium hydrogen sulfite, Sodium disulfite, sodium sulfite, sodium thiosulfate, Sodium hypophosphite, phosphorous acid, mercaptopropionic acid, Mercaptoacetic acid, mercaptoethanol and alkali metal salts of the above Acids. Mixtures of the above can of course also be used Polymerization regulators are used. If a polymerization regulator is used, the amounts used are in generally 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the monomers to be polymerized.

    Die Polymerisation kann kontinuierlich oder diskontinuierlich durchgeführt werden. Bei einer Batch-Fahrweise legt man zweckmäßigerweise Wasser als Polymerisationsmedium in einem Kessel vor, der mit Mischvorrichtung, Rückflußkühler und Wasserabscheider ausgestattet ist, erhitzt es auf die Polymerisationstemperatur und gibt nach dem Starten der Polymerisation kontinuierlich oder absatzweise das Veresterungsgemisch, Initiator und gegebenenfalls Regler zu.The polymerization can be continuous or discontinuous be performed. In the case of a batch mode of operation, it is advisable to place Water as a polymerization medium in a boiler before that with mixing device, reflux condenser and water separator equipped, it heats up to the polymerization temperature and gives continuously after starting the polymerization or batchwise the esterification mixture, initiator and if necessary regulators.

    Die Polymerisation kann bei Normaldruck, unter erhöhtem Druck oder auch unter vermindertem Druck durchgeführt werden.The polymerization can be carried out at normal pressure, under elevated pressure or can also be carried out under reduced pressure.

    Die Polymerisation erfolgt immer unter Sieden des Reaktionsgemisches.The polymerization always takes place while the reaction mixture is boiling.

    Das durch die azeotrope Abdestillation des organischen Lösungsmittels ständig mitabdestillierte Wasser wird zurückgeführt oder durch Zufuhr von frischem Wasser ersetzt. Dadurch wird gewährleistet, daß die Menge an Wasser im Reaktionsgemisch während der Polymerisation praktisch konstant bleibt und sich in der Regel 20 bis 70 gew.-%ige, vorzugsweise 30 bis 50 gew.-%ige, Polymerisatlösungen bilden. Das im Veresterungsgemisch vorliegende organische Lösungsmittel verteilt sich im Polymerisationsreaktor auf eine relativ große Fläche und wird daher rasch aus dem System entfernt, wodurch sich die oben genannte Gleichgewichtskonzentration einstellt. This is due to the azeotropic distillation of the organic solvent distilled water is returned or replaced with fresh water. This ensures that the amount of water in the reaction mixture during the Polymerization remains practically constant and usually 20 up to 70% by weight, preferably 30 to 50% by weight, polymer solutions form. The one present in the esterification mixture organic solvents are distributed in the polymerization reactor on a relatively large area and therefore quickly gets out of the system removed, causing the above equilibrium concentration established.

    Das Azeotrop wird wie bei der Veresterungsreaktion kondensiert und in zwei Phasen getrennt. Die organische Phase kann vorteilhaft bei der Veresterung wiederverwendet werden. Sollte eine Reinigung notwendig sein, so kann beispielsweise eine Flüssig-flüssig-Extraktion mit Wasser durchgeführt werden. Das organische Lösungsmittel kann zur Reinigung jedoch auch destilliert oder einer Wasserdampfdestillation unterzogen werden.The azeotrope is condensed as in the esterification reaction and separated in two phases. The organic phase can be advantageous can be reused during esterification. Should be cleaning a liquid-liquid extraction may be necessary be done with water. The organic However, solvent can also be distilled or cleaned be subjected to steam distillation.

    Bei der oben beschriebenen Batch-Fahrweise kann man die Monomeren, den Initiator und gegebenenfalls den Regler dem Reaktor in 1 bis 20 h, insbesondere in 2 bis 10 h, zuführen. Nach Beendigung der Dosierung polymerisiert man das Reaktionsgemisch üblicherweise noch 0,1 bis 10 h, bevorzugt 0,5 bis 3 h, nach. Vorzugsweise führt man die Nachpolymerisation unter Sieden des Reaktionsgemisches durch. Dabei können gegebenenfalls Reste an organischem Lösungsmittel aus dem Polymerisationsgemisch herausdestilliert werden.In the batch procedure described above, the monomers, the initiator and possibly the regulator to the reactor in FIG. 1 up to 20 h, especially in 2 to 10 h. After completion the dosage, the reaction mixture is usually polymerized still 0.1 to 10 h, preferably 0.5 to 3 h after. Preferably the postpolymerization is carried out with boiling of the reaction mixture by. If appropriate, residues of organic Distilled solvent from the polymerization mixture become.

    Nach der Polymerisation beträgt der Anteil an organischem Lösungsmittel in der wäßrigen Polymerisatlösung vorzugsweise < 100 ppm. Nach dem erfindungsgemäßen Verfahren ist es sogar möglich, das organische Lösungsmittel vollständig aus der bei der Polymerisation erhaltenen Mischung zu entfernen, so daß die Restgehalte an organischem Lösungsmittel von 0 bis 50 ppm, meistens 1 bis 30 ppm, betragen.After the polymerization, the proportion of organic Solvent in the aqueous polymer solution preferably <100 ppm. According to the method according to the invention, it is even possible the organic solvent completely from the at To remove polymerization mixture obtained, so that the residual contents of organic solvent from 0 to 50 ppm, mostly 1 up to 30 ppm.

    Um die Raum-Zeit-Ausbeute bei der Polymerisation durch ein schnelleres azeotropes Abdestillieren des organischen Lösungsmittels zu erhöhen, kann es vorteilhaft sein, Stickstoff oder Wasserdampf durch den Polymerisationsreaktor zu leiten.To the space-time yield in the polymerization by a faster azeotropic distillation of the organic solvent it may be beneficial to increase nitrogen or To conduct water vapor through the polymerization reactor.

    Zur Neutralisation des Acrylsäure als Comonomer enthaltenden Polymerisats kann man vor, während oder bevorzugt nach der Polymerisation eine Base zusetzen. Hierfür können alle basisch reagierenden Verbindungen verwendet werden. Geeignet sind z.B. Alkalimetalloxide, -hydroxide, -carbonate und -hydrogencarbonate, wobei die Kalium- und vor allem die Natriumverbindungen bevorzugt sind, Erdalkalimetalloxide und -hydroxide, insbesondere die Magnesium-, Calcium- und Bariumverbindungen, Aluminiumhydroxid, Eisenhydroxid, Eisenoxid, Ammoniak und Amine wie Cyclohexylamin, Dicyclohexylamin, Butylamin, Ethanolamin, Diethanolamin, Triethanolamin und Morpholin. Bevorzugt wird Natriumhydroxid, insbesondere in Form von 10 bis 50 gew.-%igen wäßrigen Lösungen, zur Neutralisation eingesetzt. Das Molgewicht Mw der erfindungsgemäßen Polymerisate beträgt in der Regel 1000 bis 100 000, bevorzugt 5000 bis 50 000.To neutralize the polymer containing comonomer acrylic acid, a base can be added before, during or preferably after the polymerization. All basic reacting compounds can be used for this. Suitable are, for example, alkali metal oxides, hydroxides, carbonates and hydrogen carbonates, the potassium and especially the sodium compounds being preferred, alkaline earth metal oxides and hydroxides, in particular the magnesium, calcium and barium compounds, aluminum hydroxide, iron hydroxide, iron oxide, ammonia and amines such as cyclohexylamine, dicyclohexylamine, butylamine, ethanolamine, diethanolamine, triethanolamine and morpholine. Sodium hydroxide, in particular in the form of 10 to 50% by weight aqueous solutions, is preferably used for the neutralization. The molecular weight M w of the polymers according to the invention is generally 1000 to 100,000, preferably 5000 to 50,000.

    Die erfindungsgemäßen Polymerisate eignen sich hervorragend als Zusatz für zementöse Systeme, insbesondere für Mörtel und Beton. Die Einsatzmenge der erfindungsgemäßen Polymerisate beträgt dabei üblicherweise 0,1 bis zu 5 Gew.-%, bezogen auf das zementöse System.The polymers according to the invention are outstandingly suitable as Additive for cementitious systems, especially for mortar and concrete. The amount of the polymers according to the invention used is usually 0.1 to 5 wt .-%, based on the cementitious system.

    Die erfindungsgemäßen Polymerisate haben hervorragende Wirkung als Betonverflüssiger. Sie zeigen über die gesamte Verarbeitungskette von Beton eine gleichbleibende Verflüssigungswirkung und können daher vorteilhaft in Transportbeton zum Einsatz kommen. Sie sind breit einsetzbar sowohl für verschiedene zementöse Systeme, unabhängig von deren Herkunft, Herstellung, Zusammensetzung und Zuschlägen wie Sand, Kies und Feinzuschlägen, als auch bei niedrigen und hohen Temperaturen, also im Winter und im Sommer, und unterschiedlichster Wasserqualität.The polymers according to the invention have excellent effects as a plasticizer. They show the entire processing chain of concrete a constant liquefaction effect and can therefore be used to advantage in ready-mixed concrete. They can be used widely for different cement systems, regardless of their origin, manufacture, composition and aggregates such as sand, gravel and fine aggregates, as even at low and high temperatures, i.e. in winter and in Summer, and different water quality.

    Sie können dem zementösen System als Pulver, Granulat, Schmelze oder als wäßrige Lösung (meist 30 bis 60 gew.-%ig vor, während oder nach der Mahlung zugemischt werden.You can use the cementitious system as a powder, granulate, melt or as an aqueous solution (usually 30 to 60% by weight before, during or added after grinding.

    Bei Zumischung vor der Mahlung der gebrannten Zementklinker zeigen sie gute Eigenschaften als Mahlhilfsmittel während des Mahlprozesses und bei der mechanischen Zerkleinerung des zementösen Systems.If mixed, show the fired cement clinker before grinding they have good properties as grinding aids during the grinding process and in the mechanical crushing of the cementitious System.

    BeispieleExamples A) Herstellung von erfindungsgemäßen PolymerisatenA) Preparation of polymers according to the invention

    Der Umsatz bei der Veresterung wurde NMR-spektroskopisch bestimmt. Der K-Wert der Polymerisate wurde nach H. Fikentscher, Cellulose-Chemie, Band 13, Seiten 58-64 und 71-74 (1932) in wäßriger Lösung bei einem pH-Wert von 7, einer Temperatur von 25°C und einer Konzentration des Natriumsalzes des Polymerisats von 1 Gew.-% bestimmt.The conversion in the esterification was determined by NMR spectroscopy. The K value of the polymers was determined according to H. Fikentscher, Cellulose-Chemie, Volume 13, pages 58-64 and 71-74 (1932) in aqueous Solution at a pH of 7, a temperature of 25 ° C and a concentration of the sodium salt of the polymer of 1 Wt .-% determined.

    Ester 1Ester 1

    In einem 2 1-Reaktor mit Gaseinleitungsrohr und Wasserabscheider wurde ein Gemisch aus 500 g (0,5 mol) Methylpolyethylenglykol (Mw 1000), 90 g (1,25 mol) Acrylsäure, 0,2 g Phenothiazin, 6 g p-Toluolsulfonsäurehydrat und 260 g Toluol unter Durchleiten von Stickstoff 9 h auf 135°C erhitzt (Bildung von 9 g Wasser). Die Säurezahl der bei 20°C flüssigen, lagerfähigen Veresterungsmischung betrug 50 mg KOH/g.In a 2 1 reactor with a gas inlet tube and water separator, a mixture of 500 g (0.5 mol) of methyl polyethylene glycol (M w 1000), 90 g (1.25 mol) of acrylic acid, 0.2 g of phenothiazine, 6 g of p-toluenesulfonic acid hydrate and 260 g of toluene were heated to 135 ° C. for 9 hours while passing nitrogen through (formation of 9 g of water). The acid number of the storable esterification mixture which was liquid at 20 ° C. was 50 mg KOH / g.

    Ester 2Ester 2

    Analog zur Herstellung des Esters 1 wurde ein Gemisch aus 500 g (0,5 mol) Methylpolyethylenglykol (Mw 1000), 99 g (1,375 mol) Acrylsäure, 0,2 g Phenothiazin, 6 g p-Toluolsulfonsäurehydrat und 260 g Toluol umgesetzt. Die Säurezahl der bei 20°C flüssigen, lagerfähigen Veresterungsmischung betrug 58 mg KOH/g.Analogously to the preparation of the ester 1, a mixture of 500 g (0.5 mol) of methyl polyethylene glycol (M w 1000), 99 g (1.375 mol) of acrylic acid, 0.2 g of phenothiazine, 6 g of p-toluenesulfonic acid hydrate and 260 g of toluene reacted. The acid number of the storable esterification mixture which was liquid at 20 ° C. was 58 mg KOH / g.

    Ester 3Ester 3

    Analog zur Herstellung des Esters 1 wurde ein Gemisch aus 500 g (0,5 mol) Methylpolyethylenglykol (Mw 1000), 108 g (1,5 mol) Acrylsäure, 0,2 g Phenothiazin, 6 g p-Toluolsulfonsäurehydrat und 260 g Toluol 7 h umgesetzt, bis sich kein Wasser mehr bildete. Die Säurezahl der bei 20°C flüssigen, lagerfähigen Veresterungsmischung betrug 66 mg KOH/g.Analogously to the preparation of the ester 1, a mixture of 500 g (0.5 mol) of methyl polyethylene glycol (M w 1000), 108 g (1.5 mol) of acrylic acid, 0.2 g of phenothiazine, 6 g of p-toluenesulfonic acid hydrate and 260 g of toluene 7 hours implemented until no more water formed. The acid number of the storable esterification mixture which was liquid at 20 ° C. was 66 mg KOH / g.

    Beispiel 1example 1

    In einem 2 1-Reaktor mit Gaseinleitungsrohr und Wasserabscheider wurden 450 g Wasser unter Durchleiten von Stickstoff bis zum Sieden erhitzt. Dann wurden gleichzeitig die Zuläufe 1 bis 3 gestartet: Zulauf 1: 400 g Ester 1; Zulauf 2: 53 g einer 8 gew.-%igen wäßrigen Natriumperoxodisulfatlösung; Zulauf 3: 27 g einer 10 gew.-%igen wäßrigen Natriumhydrogensulfitlösung. Zulauf 1 wurde in 6 h zudosiert, die Zuläufe 2 und 3 jeweils in 6,25 h.In a 2 1 reactor with gas inlet pipe and water separator 450 g of water were passed to the boil while passing nitrogen through heated. Then feeds 1 to 3 were started at the same time: Feed 1: 400 g of ester 1; Feed 2: 53 g of an 8% by weight aqueous sodium peroxodisulfate solution; Feed 3: 27 g of a 10 wt .-% aqueous sodium bisulfite solution. Feed 1 was metered in in 6 h, inlets 2 and 3 each in 6.25 h.

    Das Toluol wurde während der Polymerisation ständig als Azeotrop mit Wasser abdestilliert, das im Wasserabscheider in eine Wasserphase und eine Toluolphase getrennt wurde. Die Wasserphase wurde in den Polymerisationsreaktor zurückgeleitet, das Toluol wurde zur Wiederverwendung aufbewahrt. Nach Beendigung der Zuläufe wurde 1 h weiteres Wasser und restliches Toluol abdestilliert. Der Toluolrestgehalt in der Polymerisatlösung betrug < 20 ppm.The toluene was constantly azeotropic during the polymerization distilled off with water, which in the water separator into a water phase and a toluene phase was separated. The water phase was returned to the polymerization reactor, which was toluene kept for reuse. After the end of the inflows 1 hour more water and residual toluene was distilled off. The residual toluene content in the polymer solution was <20 ppm.

    Nach Abkühlen und Neutralisation mit 30 g 50 gew.-%iger Natronlauge auf pH 7 wurde eine klare 35 gew.-%ige Polymerisatlösung erhalten. Der K-Wert des Polymerisats betrug 25. After cooling and neutralization with 30 g of 50% by weight sodium hydroxide solution to pH 7 was a clear 35 wt .-% polymer solution receive. The K value of the polymer was 25.

    Beispiel 2Example 2

    Es wurde analog Beispiel 1 vorgegangen, jedoch wurden folgende Zuläufe verwendet: Zulauf 1: 400 g Ester 2; Zulauf 2: 53 g einer 5 8 gew.-%igen wäßrigen Natriumperoxodisulfatlösung; Zulauf 3: 27 g einer 12 gew.-%igen wäßrigen Natriumhydrogensulfitlösung. Es wurde eine 35 gew.-%ige Polymerisatlösung vom pH-Wert 7 erhalten. Der K-Wert des Polymerisats betrug 27.The procedure was analogous to Example 1, but the following were: Inlets used: Inlet 1: 400 g of ester 2; Feed 2: 53 g one 5 8% by weight aqueous sodium peroxodisulfate solution; Feed 3: 27 g a 12 wt .-% aqueous sodium bisulfite solution. A 35% by weight polymer solution with a pH of 7 was obtained. The K value of the polymer was 27.

    Beispiel 3Example 3

    Es wurde analog Beispiel 1 vorgegangen, jedoch wurden folgende Zuläufe verwendet: Zulauf 1: 350 g Ester 3; Zulauf 2: 48 g einer 8 gew.-%igen wäßrigen Natriumperoxodisulfatlösung; Zulauf 3: 27 g 5 einer 40 gew.-%igen wäßrigen Natriumhydrogensulfitlösung. Zur Neutralisation wurden 43 g 50 gew.-%ige Natronlauge eingesetzt. Es wurde eine 35 gew.-%ige Polymerisatlösung vom pH-Wert 6,9 erhalten. Der K-Wert des Polymerisats betrug 22.The procedure was analogous to Example 1, but the following were: Inlets used: Inlet 1: 350 g of ester 3; Inlet 2: 48 g of one 8% by weight aqueous sodium peroxodisulfate solution; Feed 3: 27 g 5 of a 40 wt .-% aqueous sodium bisulfite solution. to Neutralization was carried out using 43 g of 50% strength by weight sodium hydroxide solution. A 35% by weight polymer solution with a pH of 6.9 was obtained. The K value of the polymer was 22.

    B) Anwendung von erfindungsgemäßen PolymerisatenB) Use of polymers according to the invention

    Anhand des Mörteltests gemäß DIN 1164 bzw. EN 196 wurde die Zement dispergierende Wirkung der Polymerisate aus Beispiel 1 bis 3 untersucht.Based on the mortar test according to DIN 1164 or EN 196, the cement was dispersing effect of the polymers from Examples 1 to 3 examined.

    Die Einsatzmengen betrugen:

  • 500 g Heidelberger Zement CEM I 32,5 R
  • 1350 g CEN-Normsand
  • 225 g Trinkwasser
  • 0,15 Gew.-% Polymerisat, berechnet Feststoffgehalt auf die verwendete Menge Zement, d.h. 0,75 g Polymer
  • 0,35 Gew.-% eines handelsüblichen Entschäumers auf Basis von Phosphorsäureestern, bezogen auf das Polymerisat.
    • The amounts used were:
  • 500 g Heidelberg cement CEM I 32.5 R
  • 1350 g of CEN standard sand
  • 225 g drinking water
  • 0.15% by weight of polymer, calculated solids content based on the amount of cement used, ie 0.75 g of polymer
  • 0.35% by weight of a commercially available defoamer based on phosphoric acid esters, based on the polymer.

    • In der folgenden Tabelle ist die verflüssigende Wirkung der Polymerisate auf die Mörtelmischung anhand der Ausbreitmaße nach 1, 30 und 60 min dargestellt. Polymerisat aus Bsp. Ausbreitmaß in cm gemäß DIN 1164 nach 1 min 30 min 60 min 1 17,3 17,0 15,7 2 17,7 18,7 16,4 3 18,2 18,4 16,1 The table below shows the plasticizing effect of the polymers on the mortar mixture based on the slump after 1, 30 and 60 min. Polymer from Ex. Spread in cm according to DIN 1164 1 min 30 min 60 min 1 17.3 17.0 15.7 2 17.7 18.7 16.4 3 18.2 18.4 16.1

    Claims (10)

    Wasserlösliche Polymerisate von Estern aus Acrylsäure und Al-5 kylpolyalkylenglykolen, erhältlich durch azeotrope Veresterung einer Mischung von Acrylsäure und Alkylpolyalkylenglykol im Molverhältnis von 2 bis 3 : 1 in Gegenwart eines organischen Lösungsmittels, das mit Wasser ein Azeotrop bildet, zu mindestens 85 Gew.-%, bezogen auf das Alkylpolyalkylenglykol, und anschließende radikalische Polymerisation des bei der Veresterung erhaltenen Gemisches in wäßrigem Medium, wobei man das organische Lösungsmittel während der Polymerisation azeotrop aus dem Reaktionsgemisch abdestilliert und das abdestillierte Wasser in das Gemisch zurückführt oder durch Zufuhr von frischem Wasser ersetzt.Water-soluble polymers of esters from acrylic acid and Al-5 alkyl polyalkylene glycols, obtainable by azeotropic esterification a mixture of acrylic acid and alkyl polyalkylene glycol in a molar ratio of 2 to 3: 1 in the presence of an organic Solvent that forms an azeotrope with water at least 85% by weight, based on the alkyl polyalkylene glycol, and subsequent free radical polymerization of the Esterification obtained mixture in aqueous medium, wherein the organic solvent during the polymerization Distilled off azeotropically from the reaction mixture and the distilled off Water is returned to the mixture or by feeding replaced by fresh water. Polymerisate nach Anspruch 1, bei denen als Alkylpolyalkylenglykol ein Methylpolyalkylenglykol oder eine Mischung verschiedener Methylpolyalkylenglykole eingesetzt wird.Polymers according to claim 1, in which the alkyl polyalkylene glycol a methyl polyalkylene glycol or a mixture of different Methyl polyalkylene glycols is used. Polymerisate nach Anspruch 1 oder 2, bei denen als Alkylpolyalkylenglykol ein Methylpolyethylenglykol der Molmasse Mw 350 bis 4000 oder eine Mischung dieser Methylpolyethylenglykole eingesetzt wird.Polymers according to Claim 1 or 2, in which a methylpolyethylene glycol of molecular weight M w 350 to 4000 or a mixture of these methylpolyethylene glycols is used as the alkyl polyalkylene glycol. Polymerisate nach den Ansprüchen 1 bis 3, bei denen der Gehalt an organischem Lösungsmittel im erhaltenen Veresterungsgemisch vor der Polymerisation < 40 Gew.-% beträgt.Polymers according to claims 1 to 3, in which the Organic solvent content in the esterification mixture obtained before polymerization is <40% by weight. Polymerisate nach den Ansprüchen 1 bis 4, bei denen die Säuregruppen nach, während oder vor der Polymerisation zumindest teilweise mit Basen neutralisiert werden.Polymers according to claims 1 to 4, in which the At least acid groups after, during or before the polymerization partially neutralized with bases. Polymerisate nach den Ansprüchen 1 bis 5, bei denen die Polymerisation in Gegenwart von 0,1 bis 10 Gew.-% Polymerisationsregler, bezogen auf die zu polymerisierenden Monomere, durchgeführt wird.Polymers according to claims 1 to 5, in which the Polymerization in the presence of 0.1 to 10% by weight of polymerization regulator, based on the monomers to be polymerized, is carried out. Verfahren zur Herstellung von wasserlöslichen Polymerisaten von Estern aus Acrylsäure und Alkylpolyalkylenglykolen, dadurch gekennzeichnet, daß man es nach den Verfahrensschritten gemäß Anspruch 1 vornimmt.A process for the preparation of water-soluble polymers of esters from acrylic acid and alkylpolyalkylene glycols, characterized in that it is carried out according to the process steps according to claim 1. Verwendung von wasserlöslichen Polymerisaten gemäß den Ansprüchen 1 bis 6 als Zusatz zu zementösen Systemen. Use of water-soluble polymers according to the claims 1 to 6 as an addition to cementitious systems. Verwendung von wasserlöslichen Polymerisaten gemäß den Ansprüchen 1 bis 6 als Verflüssiger für wasserhaltige zementöse Systeme.Use of water-soluble polymers according to the claims 1 to 6 as a plasticizer for water-based cementitious Systems. Verwendung von wasserlöslichen Polymerisaten gemäß den Ansprüchen 1 bis 6 als Mahlhilfsmittel für zementöse Systeme.Use of water-soluble polymers according to the claims 1 to 6 as grinding aids for cementitious systems.
    EP02009116A 2001-05-22 2002-04-24 Use of water-soluble polymers from esters of acrylic acid and alkylpolyalkylene glycols as milling agents for cement. Expired - Lifetime EP1260535B1 (en)

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    DE10125237A DE10125237A1 (en) 2001-05-22 2001-05-22 Water-soluble polymers of esters from acrylic acid and alkyl polyalkylene glycols
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    EP1577372A1 (en) * 2004-03-19 2005-09-21 Sika Technology AG Stable aqueous dispersion of particles , its use and its process of production
    WO2005123621A1 (en) 2004-06-21 2005-12-29 Sika Technology Ag Cement grinding aid
    WO2007063030A2 (en) * 2005-12-02 2007-06-07 Basf Se Use of comb polymers as a grinding agent for preparations containing cement
    WO2010074805A1 (en) * 2008-12-23 2010-07-01 E. I. Du Pont De Nemours And Company Process for the production of acrylic and methacrylic esters of poly(trimethylene ether) glycol
    EP2574636A1 (en) * 2011-09-30 2013-04-03 BASF Construction Polymers GmbH Quickly suspending power-form compound
    WO2022262985A1 (en) * 2021-06-17 2022-12-22 Cemex Innovation Holding Ag Robust polycarboxylate with polyalkylene oxide-based sacrificial sidechain linkage as milling aid for cementitious materials

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    CN101671142B (en) * 2009-10-13 2012-09-26 王涛 Cement reinforced grinding aid prepared with hydrolyzed polymaleic acid
    CN101798198B (en) * 2010-04-03 2012-11-21 山东宏艺科技股份有限公司 Polycarboxylic acid cement activation reinforced grinding aid and preparation method thereof
    CN102153308B (en) * 2011-05-17 2012-08-08 北京金隅水泥节能科技有限公司 Cement liquid grinding aid and preparation method thereof
    CN112358609B (en) * 2020-11-18 2023-05-02 长江大学 Citric acid polyethylene glycol monoester and preparation method and application thereof

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    EP1577372A1 (en) * 2004-03-19 2005-09-21 Sika Technology AG Stable aqueous dispersion of particles , its use and its process of production
    WO2005090533A1 (en) * 2004-03-19 2005-09-29 Sika Technology Ag Stable aqueous particle dispersion the use thereof and method for producing said dispersion
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    WO2010074805A1 (en) * 2008-12-23 2010-07-01 E. I. Du Pont De Nemours And Company Process for the production of acrylic and methacrylic esters of poly(trimethylene ether) glycol
    EP2574636A1 (en) * 2011-09-30 2013-04-03 BASF Construction Polymers GmbH Quickly suspending power-form compound
    WO2013045419A1 (en) * 2011-09-30 2013-04-04 Basf Construction Polymers Gmbh Powder composition for rapid suspension
    CN103857712A (en) * 2011-09-30 2014-06-11 巴斯夫建筑方案股份有限公司 Powder composition for rapid suspension
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    WO2022262985A1 (en) * 2021-06-17 2022-12-22 Cemex Innovation Holding Ag Robust polycarboxylate with polyalkylene oxide-based sacrificial sidechain linkage as milling aid for cementitious materials

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    JP4167005B2 (en) 2008-10-15
    JP2003096147A (en) 2003-04-03
    ES2289025T3 (en) 2008-02-01
    DE50210438D1 (en) 2007-08-23
    DE10125237A1 (en) 2002-11-28
    US6849703B2 (en) 2005-02-01
    ATE366768T1 (en) 2007-08-15
    BR0201893A (en) 2004-04-13
    EP1260535B1 (en) 2007-07-11
    US20020188093A1 (en) 2002-12-12

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